阅读说明：本技术 一种无溶剂5-羟甲基糠醛制备2,5-呋喃二甲醇的方法 (Method for preparing 2, 5-furandimethanol from solvent-free 5-hydroxymethylfurfural ) 是由 唐兴 王婷 孙勇 曾宪海 林鹿 雷廷宙 于 2019-09-29 设计创作，主要内容包括：本发明公开了一种无溶剂5-羟甲基糠醛制备2,5-呋喃二甲醇的方法,本发明应用金属催化剂,以氢气为氢供体,通过改变氢键受体或调控氢键受体及5-羟基糠醛(氢键供体)间的摩尔比例,改变氢键受体与底物间的氢键作用强度,达到高温下稳定底物及产物的目的,实现无溶剂5-羟甲基糠醛加氢合成2,5-呋喃二甲醇。(The invention discloses a method for preparing 2, 5-furandimethanol from solvent-free 5-hydroxymethylfurfural, which applies a metal catalyst, takes hydrogen as a hydrogen donor, changes the hydrogen bond action strength between a hydrogen bond acceptor and a substrate by changing the hydrogen bond acceptor or regulating the molar ratio between the hydrogen bond acceptor and 5-hydroxymethylfurfural (hydrogen bond donor), achieves the aim of stabilizing the substrate and a product at high temperature, and realizes the synthesis of the 2, 5-furandimethanol from the solvent-free 5-hydroxymethylfurfural through hydrogenation.)

1. A method for preparing 2, 5-furandimethanol from solvent-free 5-hydroxymethylfurfural is characterized by comprising the following steps: the method comprises the following steps: mixing a salt hydrogen bond donor and 5-hydroxymethylfurfural to form a uniform and clear eutectic mixture, filling the eutectic mixture into a high-pressure reaction kettle, adding a catalyst, introducing hydrogen, and carrying out closed reaction for 1-3h at 80-140 ℃ and under the pressure of 3-6MPa to obtain 2, 5-furandimethanol; the salt hydrogen bond donor comprises at least one of zinc chloride, choline chloride and choline bromide, and the catalyst comprises at least one of Raney cobalt, Raney copper, Ru/C, Pd/C and Pt/C.

2. The method of claim 1, wherein: the salt hydrogen bond donor is zinc chloride, choline chloride or choline bromide.

3. The method of claim 1, wherein: the catalyst is Raney cobalt, Raney copper, Ru/C, Pd/C or Pt/C.

4. The method of claim 1, wherein: the salt hydrogen bond donor is zinc chloride, choline chloride or choline bromide; the catalyst is Raney cobalt, Raney copper, Ru/C, Pd/C or Pt/C.

5. The method of any of claims 1 to 4, wherein: the molar ratio of the salt hydrogen bond donor to the 5-hydroxymethylfurfural is 1: 1-40.

6. The method of claim 5, wherein: the molar ratio of the salt hydrogen bond donor to the 5-hydroxymethylfurfural is 1: 2-40.

Technical Field

The invention belongs to the technical field of organic catalytic synthesis, and particularly relates to a method for preparing 2, 5-furandimethanol from solvent-free 5-hydroxymethylfurfural.

Background

In recent years, the conversion of renewable biomass resources into high value-added bio-based chemicals has become an important way to reduce the over-dependence on non-renewable fossil resources in today's society. Among them, 5-hydroxymethylfurfural is useful for preparing a series of derivatives that are of high quality and can partially replace stone-based products, and thus, it is considered to be one of ten major platform compounds based on biomass resources. Wherein, the 2, 5-furan dimethanol can be prepared from 5-hydroxymethyl furfural, and has wider application prospect as an important biomass-based chemical. The 2, 5-furandimethanol can be used as an important intermediate for preparing high-value chemicals such as 2, 5-furandimethanol, 2, 5-dimethylol tetrahydrofuran, 1, 6-hexanediol and the like. The 2, 5-furandimethanol can also be used as a structural monomer to produce heat insulation materials, resin materials, crown ether materials and the like. Meanwhile, it can also be used for preparing memory materials and high molecular polymer materials with self-repairing function. 2, 5-furandimethanol is also useful in the synthesis of pharmaceutical intermediates and nucleoside derivatives, which themselves may also serve as artificial receptors in the study of molecular recognition.

As is known, 5-hydroxymethylfurfural molecules simultaneously contain an aldehyde functional group, an alcoholic hydroxyl functional group and a furan ring functional group, so that the chemical properties of the 5-hydroxymethylfurfural are very active, the 5-hydroxymethylfurfural is easy to generate a polymerization reaction under high concentration to form humus, and the product generated in the hydrogenation reaction is relatively complex, so that the problem that the first solution is needed in the process of synthesizing 2, 5-furandimethanol by selective hydrogenation of 5-hydroxymethylfurfural is solved by avoiding the polymerization of 5-hydroxymethylfurfural under high concentration reaction and ensuring the preferential hydrogenation of aldehyde groups, and the excessive hydrogenation of alcoholic hydroxyl and furan rings is avoided as much as possible, and the development of a proper reaction system plays a crucial role in solving the problem.

CN 106316994A discloses a method for simultaneously preparing and separating 2, 5-furan dicarbaldehyde and 2, 5-furan dimethanol. The method adopts Lewis acid catalyst to simultaneously obtain 2, 5-furan dicarbaldehyde and 2, 5-furan dimethanol through MPVO reaction. The method has high product selectivity (100%), but low 5-hydroxymethylfurfural conversion rate (40%), and the concentration of the product is only 0.63g/ml at most. In addition, the reaction solvent is tetrahydrofuran, dimethyl sulfoxide, dimethylformamide, dioxane, dimethyl sulfoxide, acetonitrile, toluene and dichloroethane, and particularly has high toxicity. The method adopts segmented heating, and the heating times are 3-12 times, so that the operation complexity is increased.

CN105289619A discloses a nickel-based catalyst, a preparation method thereof and application thereof in catalyzing hydrogenation of 5-hydroxymethylfurfural. Under the catalytic action of a nickel-based catalyst, the 5-hydroxymethylfurfural is subjected to hydrogenation reaction to prepare 2, 5-dimethylfuran or 2, 5-dimethyltetrahydrofuran. The method avoids using a noble metal catalyst for hydrodeoxygenation, saves the cost of the catalyst, but has higher reaction temperature (higher than 160 ℃) and can not inhibit hydrogenation on furan rings, and the selectivity of 2, 5-dimethylfuran is lower.

CN 107442177A discloses a method for synthesizing 2, 5-furandimethanol by selective hydrogenation of 5-hydroxymethylfurfural. The method takes a magnetic metal organic coordination polymer as an acid-base bifunctional catalyst, 5-hydroxymethylfurfural is efficiently converted into 2, 5-furandimethanol through selective transfer hydrogenation reaction, and the highest yield can reach 98.6%. However, the concentration of 5-hydroxymethylfurfural is lower at 1-3 wt%.

In addition, in the research of preparing 2, 5-furandimethanol from 5-hydroxymethylfurfural, metal catalysts (such as Pt, Pd and Ru-based noble metal catalysts and non-noble metal catalysts such as Cu, Co, Ni and Zr) are mainly adopted, 2, 5-furandimethanol can be obtained at high selectivity, however, the concentrations of substrates and products in a reaction system are relatively low (< 25 wt%). Therefore, it is of great significance to explore and develop a method for preparing 2, 5-furandimethanol by high-selectivity high-concentration catalytic conversion of 5-hydroxymethylfurfural.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provides a method for preparing 2, 5-furandimethanol from solvent-free 5-hydroxymethylfurfural.

The technical scheme of the invention is as follows:

a method for preparing 2, 5-furandimethanol from solvent-free 5-hydroxymethylfurfural, comprising: mixing a salt hydrogen bond donor and 5-hydroxymethylfurfural to form a uniform and clear eutectic mixture, filling the eutectic mixture into a high-pressure reaction kettle, adding a catalyst, introducing hydrogen, and carrying out closed reaction for 1-3h at 80-140 ℃ and under the pressure of 3-6MPa to obtain 2, 5-furandimethanol;

the salt hydrogen bond donor comprises at least one of zinc chloride, choline chloride and choline bromide, and the catalyst comprises at least one of Raney cobalt, Raney copper, Ru/C, Pd/C and Pt/C.

In a preferred embodiment of the present invention, the salt-type hydrogen bond donor is zinc chloride, choline chloride or choline bromide.

In a preferred embodiment of the invention, the catalyst is Raney cobalt, Raney copper, Ru/C, Pd/C or Pt/C.

In a preferred embodiment of the present invention, the salt-type hydrogen bond donor is zinc chloride, choline chloride or choline bromide; the catalyst is Raney cobalt, Raney copper, Ru/C, Pd/C or Pt/C.

In a preferred embodiment of the invention, the molar ratio of the salt hydrogen bond donor to the 5-hydroxymethylfurfural is 1: 1-40.

Further preferably, the molar ratio of the salt hydrogen bond donor to the 5-hydroxymethylfurfural is 1: 2-40.

The invention has the beneficial effects that: the invention uses metal catalyst, hydrogen as hydrogen donor, and changes the hydrogen bond strength between hydrogen bond acceptor and substrate by changing hydrogen bond acceptor or regulating the molar ratio between hydrogen bond acceptor and 5-hydroxy furfural (hydrogen bond donor), so as to stabilize substrate and product at high temperature, and realize the hydrogenation synthesis of 2, 5-furandimethanol by solvent-free 5-hydroxy methylfurfural.

Detailed Description

The technical solution of the present invention is further illustrated and described by the following detailed description.